Haloorgano silcarbane siloxanes



United States Patent HALOORGANO SILCARBANE SILOXANES Donald D. Smith,Midland, Mich., assignor to Dow Cornlug Corporation, Midland, Mich., acorporation of Michigan No Drawing. Application March 7, 1957 Serial No.644,445

6 Claims. (Cl. 260-448.2)

This invention relates to siloxanes derived from monovinyl silaneshaving a halogenated cyclobutyl group, a

trifluoropropyl group, a trifluorotolyl group, or a hexafluoroisohexylgroup on the silicon.

More specifically this invention relates to a compound of the formula[XS1(GH2)2S1 1O R is selected from the group consisting of aryl, alkyl,and cycloalkyl hydrocarbon radicals and X is selected from the groupconsisting of CF CH CH omornom ia oma cyclobutyl group of the formulaCJ-I F Cland CF; cmcmcmonomortho-, meta-, and para-trifiuorotolylradicals,

C F C10 FrOHalIEP- EFzCF CICHzLH- The chlorotrifluorocyclobutyl radicalsare best attached to silicon as shown in the copending application ofArthur F. Gordon, Serial No. 494,287, filed March 14, 1955. The CF CH CHand and C F a CFrCHzCHzCHQGH: radicals are best attached to silicon byreacting the correwhere the organic radicals are defined by R above.This reaction is best accomplished by cautiously heating the vinylsilaneto 100 C. (or its boiling point if less than 100 C.) with a catalystsuch as platinum on charcoal or chloroplatinic acid in dimethylcarbitoluntil the reaction becomes spontaneous and maintaining the reactiontemperature between 150-175 C.

Another method of preparation is employing the above Grignard reactionto form a monovinyl silane R xs1orr=om) which is reacted with adiorganomonohalo'silane Y RaSiH to form the silylethylmonohalosilane R2R2 (XSiCHflCHISl-Y) which can be hydrolyzed and condensed to form thesilylethyldisiloxane R: R: (xsiomcmsmo Alternatively, one may prepare asilane of the formula R2 CHz=OHSiY where R and Y are as above definedand subsequently react it with a silane of the formula R2 XSiH where Xand R are as above defined to produce R2 R2 XSiOHzCHzSiY which can behydrolyzed and condensed to the disiloxane. In this method the R2CHz=CHSiY silanes may first be condensed to disiloxanes before reactionwith the R2 XSiH silane.

If desired, any of the above hydrolyses can be carried out in thepresence of an inert solvent such as benzene,

' toluene, ether, and the like.

spending olefins with the desired SiH compound at an a elevatedtemperature. 'Ihesilylethylsiloxanes of this invention are preferablyprepared by reacting silanes of the formula where X and R are as abovedefined and Y is a hydrolyz- I able group such as a halogen, e. g.chlorine, bromine, and iodine, or an alkoxy group, e. g. methoxy andbutoxy, with vinyl Grignard to form a monovinyl silane. A preferredmethod for the preparation of vinyl Grignard re- 2 R2 R2 (1.6. HBlOSlH)In the silanes and dihydrodisiloxanes used as starting materials it isnecessary that the non-reacting organic radicals be limited to R asabove defined to prevent extraneous and deleterious side reactions.

This invention also relates to copolymers of from 0.1 to 'mo1 percent of(1) the siloxanes of this invention and from 20 to 99.9 mol percent of(2) compositions of the unit formula where Z can be any monovalenthydrocarbon radical or any halogenated derivative thereof, and m has anaverage value of from 0 to 3 inclusive. In said copolymers the totalnumber of Z groups and (1) siloxane units per silicon atom of (2) is atleast 1.

These copolymers can be prepared by any means of copolymerization suchas cohydrolyzing a mixture of haloor alkoxy-s'ilanes of the formulae andZ SiY where X, R, Z, Y, and m are as above defined. Another method ofpreparation of the copoly- 1 mers of this'invention is catalyticcopolymerization of the siloxanes of this invention with siloxanes ofthe formula preferably in the presence of an acid catalyst.

Z can be alkyl, e. g. methyl, 2-ethyl-hexyl and octadecyl; cycloalkyl,e. g. cyclohexyl and cyclopentyl; halogenated alkyl, e. g.2,3-dibromopropyl and 4-trifluoromethyldecyl; halogenated cycloalkyl, e.g. 2,4,6-triiodocyclohexyl; aryl, e. g. phenyl, xenyl and naphthyl;halogenated aryl, e. g. 2,4-dichlorophenyl, fl-bromonaphthyl, andbromoxenyl; aralkyl, e. g. benzyl; halogenated aralkyl, e. g.oz-chlorobenzyl and 2,4-dichlorobenzyl; alkaryl, e. g. tolyl;halogenated alkaryl, e. g. trifiuorotolyl; alkenyl, e. g. vinyl, allyland 5,6-octadecenyl; rcycloalkenyl, e. g. 2,3-cyclopentenyl; halogenatedalkenyl, e. g. 3-iodoallyl and symdibromovinyl; and halogenatedcycloalkenyl, e. g. 4,5-dichloro-2,3-cyclohexenyl. Z can also be any ofthe groups defined by X.

The siloxanes or this invention are especially useful as lubricants andmay also be used for coatings, elastomers and molding resins.

The following examples are illustrative only and should not be construedas limiting the invention which is properly set forth in the appendedclaims.

Example 1 was dissolved in an equal volume of tetrahydrofuran, and thesolution was added slowly with stirring to a solution of vinyl Grignardin tetrahydrofuran in a ratio of one mol of silane per mol of Grignardreagent. During the reaction the reaction flask Was cooled by an icewater bath. When the silane addition was complete, the reaction mixturewas allowed to warm to room temperature. The contents of the reactionflask were poured into an ice water mixture, and hydrochloric acid wasadded to dissolve magnesium salts. The organic layer was separated,washed with water several times to remove most of the tetrahydrofuran,and dried with calcium hydride. The dried organic layer was distilledand a 72% yield of chlorotrifluorocyclobutylvinyldimethylsilane wasobtained. This product had the following properties:

(b) This silane was heated to 100 C. with 0.06% platinum on charcoal sothat there was one gram of catalyst per mol of silane.Sym-tetramethyldisiloxane was added slowly so that the temperature ofthe spontaneous reaction was maintained in the range 150-175 C. untilthe addition was complete. The reaction mixture was cooled, diluted withether and filtered. The ether was removed by distillation at atmosphericpressure. The residual fluid was heated to 150 C. at a pressure ofapproximately 1 mm. Hg to remove low molecular weight materials and wasrefiltered. The product was a fluid disiloxane of the formula Me: Me:FClCFzCHa HSl(CHz)2Si O Load Soar 4 Example 2 When3,3,3-trifluoropropyldimethylmethoxysilane, p a,oc,octrifluorotolyldimethylchlorosilane, and5,5,5-trifluor0-2-trifluoromethylamyldimethylchlorosilane wassubstituted for the chlorosilane in Example 1(a), the correspondingvinylsilanes and silylethyldisiloxanes resulted:

CF; Mel OFsCH2CH:CHGHzSiCH=GHI Me: Me: [O FaCH:CH:Si(CH:)2Si 10 Me: Me:[om-Osxcmnsr ]o and The disiloxanes were suitable as lubricants.

Example 3 When monochlorodirnethylsilane was substituted for thesym-tetramethyldisiloxane of Example 1(b) and the resulting product washydrolyzed, a fluid disiloxane of the formula Mei Mes [OFClOF CHLHSKCHzhSl 0 Example 4 resulted.

and

81-0- (EH=CH: units.

Example 5 When p-a,a,a-trifluorotolyl-2-ethyl-hexylnaphthylvinylsilaneand dixenylmonoethoxysilane are reacted in accordance with the method ofExample 1 in a molar ratio of 1:1 and the reaction product is hydrolyzedand condensed with bis-3,3,3-trifluoropropyldiethoxysilane in a molarratio of one mol of the reaction product to three mols of thediethoxysilane, the resulting thermoplasticcopolymer consists ofSKC-Hdr-SlO- -OH-(CE) a-Me units.

which consists of (CHaCHaCFt): 1 0....

Example 6 l When 5,5,5 trifluoro 2 trifluoromethylamylditolylvinylsilaneand dicyclohexyhnonochlorosilane are reacted accordance with the methodof Example 1 in a molar ratio of 1:1 and the reaction product ishydrolyzed and condensed withtoly1 2,3cyclopentenyl-Z-ethyl-hexylchorosilane in a molar ratio of 1:1, aflu'idcopolymer rei OF: 2

OFKQHIh-bH-CILBKCHQ:- l t Example 7 When 3,3,3trifluoropropylphenylbutylvinylsilane and methylnaphthylmonochlorosilaneare reacted in accordance with the method of Example 1 in a molar ratioof 1:1 and the reaction product is hydrolyzed and condensed with silicontetrachloride in a molar ratio of four mols of the reaction product toone mol of silicon tetrachloride, there results a fluid copolymer of theformula units.

Ph Me O FlCH:CH2%iCH2CH2SlO- Si Example 8 When butyl 8, ,'y-trifiuoro-8-chlorocyclobutylphenylvinylsilane and dimethylmonochlorosilane arereacted in accordance with the method of Example 1 in a molar ratio of1:1 and the reaction product is hydrolyzed and condensed withbenzyltrichlorosilane in a molar ratio of three mols of the reactionproduct to one mol of the trichlorosilane, a fluid copolymer resultswhich consists of Bu FClCFrCHa HSPigHiCHzSl(Me);O-]

Example 9 When an equimolar mixture oftrifluorotolyldimethylvinylsilane, 5, trifiuoro Bchlorocyclobutyldiphenylvinylsilane, phenylbutylmonochlorosilane, and2-ethy1- hexyhtenylmonochlorosilane is reacted in accordance with themethod of Example 1 and the reaction product is hydrolyzed and condensedwith an equimolar mixture of and units.

'cyclohexyltrichlorosilane, phenyl-2-ethyl-6-hromo-hexy1-amylchlorosilane, tolylbenzyldichlorosilane and silicon tetrachloride, acopolymer results which ci'snsists mol percent of each of the followingunit's:

Me: @SKCHahSiO- omginonmua W 91i), P11 FCICFsCHs suomnsggand monr-cmonmomnr] PhSlO- (CHmMe That which is claimed is: 1. A compound ofthe formula R: R2 [XSKCHmSi 10 where R is selected from the groupconsisting of aryl, alkyl, and cycloalkyl hydrocarbon radicals and X isselected from the group consisting of CF CH CH C F: OFaCHaCHsCHCHa- 2. Acompound of the formula and Me: Me: [crlcnlcmsucmnsi 10 3. A compound ofthe formula 01!; Me, Me: cmomcmcflcmsucmhsl 10 4. A compound of theformula Me: Me:

FYCFYCH: HSKCHmSl O where one Y is fluorine and the other Y is chlorine.

5. A compound of the formula 1165Azcopolymercomprismgfrom to 80 11101percent of 1) sil'oxane .of the formula where R is selected from zthegroup consisting of aryl,

[X5 130 Hzh i O .5] 7

alkyl, and cycloalkyl hydrocarbon radicals and where X is selected fromthe group consisting of CF CH CH and CF; CFaCHnCHaCHCHrwhere Z isselected from the group consisting of monovalent hydrocarbon radicalsand their halogenated derivafives, m has an average value from 0 to 3inclusive, in .whichlcopolymer the total number of Z groups and (1),s'iloxanetunits per silicon atom in (2) is at least 1.

References Cited in the file of this patent UNITED STATES PATENTS2,511,056 Goodwin June 13, 195 0 FOREIGN PATENTS 1,116,316

France Jan. 30, 1956

1. A COMPOUND OF THE FORMULA